KR19980080506A - Fluorine grease - Google Patents

Abstract

The disclosed subject matter includes 15-50% by weight of a tetrafluoroethylene copolymer with monomers unsaturated with polytetrafluoroethylene or other ethylene; 30-84.5% by weight of perfluoroether oil having a viscosity comprised between 20 and 4000 cst at 20 ° C; 0.5-10% by weight of a surfactant or dispersant having a perfluoropolyether or perfluoroalkyl chain; And at least 0-10% by weight of an anticorrosion and / or antiwear additive, wherein the (per) fluoropolymer particles or their totals based on the tetrafluoroethylene have an average size smaller than microns, A fluorine grease exhibiting an improved diameter wear value.

Description

Fluorine grease

FIELD OF THE INVENTION The present invention relates to greases or lubricating pastes based on perfluoropolyethers (hereinafter referred to as PFPE) and fluorinated polymers, in particular tetrafluoroethylene polymers [or polytetrafluoroethylene] PTFE) or greases or lubricating pastes based on tetrafluoroethylene copolymers (TFE copolymers) having monomers which are wholly or partly fluorinated with other ethylene unsaturated monomers.

It is known that fluorine grease is prepared by suspending polytetrafluoroethylene polymers in perfluorinated liquids such as perfluoropolyethers. For example, J. Messina J. Am. Soc of Lubr. See 475-481 and USP 4,472,290 to Eng (Dec. 1996). PTFE polymers generally have a 7% by weight suspension in 1,1,2-trichlorotrifluoroethane. The grease method is achieved by slowly adding PFPE to a 7% PTFE suspension by evaporating the solvent simultaneously under vacuum.

This process is very long and delicate and requires the use of a volume of polymer suspension of up to about 50 liters, in particular for producing about 30 kg of grease. This process is also no longer useful due to legal sanctions on the use of chlorofluorocarbons (CFCs).

Current methods for producing greases are based on dispersion in PFPE with dry powders of fluoropolymers. In fact, a disadvantage of this technique is that dry powder is formed by coagulation so that a finish is required to homogenize the system in order to reduce the coagulation size and achieve the desired lubricating properties.

In particular, USP 4,472,290, three times in a grinder to heat PTFE powder under vacuum, to heat PTFE oil and additives under vacuum, to slowly mix the components under vacuum, to cool at room temperature and to reduce solidification and homogenize the system. Methods of making lubricating greases based on PTFE and perfluoropolyethers, which consist of a rotating finish, are known.

These methods are complex and have the disadvantage of requiring careful attention in the three grinding processes, for example in the handling of conditions such as rotation speed and distance between rotations.

Greases obtained through the process described in this patent are generally as follows: 15-40% by weight PTFE, 60-85% by weight liquid PFPE, less than 1% perfluoroalkyl or polyoxyperfluoroalkyl surfactants and stabilizers And optional additives such as corrosion inhibitors. Such additives are known to change the grease component, see for example USP 5,000,864.

There is a need to use improved greases based on TFE (co) polymers which exhibit improved lubricity, in particular wear resistance values, and a mixture of properties such as low oil separation and low volatility.

It is an object of the present invention to provide fluorine grease.

Another object of the present invention is to provide a method for producing fluorine grease.

Features of the present invention are 15 to 50% by weight of a tetratetrafluoroethylene or tetrafluoroethylene copolymer having monomers fully or partially fluorine and unsaturated with other ethylene;

30-84.5% by weight of perfluoroether oil having a viscosity comprised between 20 and 4000 cst at 20 ° C;

0.5-10% by weight of a surfactant or dispersant having a perfluoropolyether or perfluoroalkyl chain; And

At least 0-10% by weight of the anti-corrosion and / or wear resistant additives,

The wear diameter values of the fluorine greases having the same composition as those of the (per) fluoropolymer particles or the total thereof based on the TFE have a smaller average size than microns, and the wear diameters of the conventional fluorine greases having the same components as the preparations. In fluorine grease at least 25% lower than the value.

Preferably, the fluorine grease, which is the object of the present invention, contains at least 15 to 30% by weight of the above polytetrafluoroethylene or copolymers thereof.

Tetrafluoroethylene copolymers are for example the following:

A) perfluoroalkylperfluorovinylethers such as, for example, methylvinylether and propylvinylether; Vinyldene fluoride; Hexafluoroisobutene; Chlorotrifluoroethylene; One or more comonomers selected from perfluoroalkylethylene such as, for example, perfluoropropene, modified polytetrafluoroethylene comprising a small amount generally comprised between 0.01 and 3 mol%, preferably between 0.05 and 0.5 mol% and;

B) at least 0.5 to 8 mol% of perfluoroalkyl vinyl ethers, wherein the perfluoroalkyl radicals comprise 1 to 6 carbon atoms, for example TFE / perfluoropropylvinyl ether, TFE / Tetrafluoroethylene (TFE) thermoplastic copolymers such as perfluoromethylvinylether, TFE / perfluoroethylvinylether, TFE / perfluoroalkylethylene copolymer;

C) a small amount (less than 5 mol%) of other comonos comprising from 2 to 20 mol% of perfluoroolefin C ₃ -C ₈ and having a perfluorovinyl ether structure (see eg USP 4,675,380, above). ) Can be added, for example tetrafluoroethylene thermoplastic copolymers such as TFE / hexafluoropropene copolymers;

D) a tetrafluoroethylene thermoplastic (co) polymer comprising 0.5-13% by weight of perfluoromethylvinyl ether and 0.05-5% by weight of one or more fluorine monomers selected from the following groups 1), 2), 3) May be mentioned.

Groups 1), 2) and 3) in D) are as follows.

First, the group 1) is R _F O-CF = CF ₂ (II),

Where R _F is:

V) perfluoroalkyl radicals containing from 2 to 12 carbon atoms;

Ii)-(CF ₂ -CF (CF ₃ ) -O) _r- (CF ₂ ) _{r '} -CF ₃ (III),

R is an integer comprised between 1 and 4, and r 'is an integer comprised between 0 and 3;

Iii) as -Z (OCFX) _q (OCF ₂ -CFY) _{q '} -OT (IV),

Wherein the units (OCFX) and (OCF ₂ -CFY) are statistically distributed along the chain;

T is a (per) fluoroalkyl radical having from 1 to 3 carbon atoms and optionally comprises H or Cl atoms;

X and Y are the same as -F or -CF ₃ ; Z represents-(CFX)-or-(CF ₂ -CFY)-;

Equal to or different from each other, q and q 'are integers constituting between 0 and 10;

The weight average molecular weight of the monomer is comprised between 200 and 2000;

2) group is R _F -CH = CF ₂ (Ⅶ),

R _F is the meaning described in the group 1);

3) The group is preferably a perfluorodioxol having the formula

(Ⅷ)

In which R ₃ is perfluoroalkyl radical C ₁ -C ₅ , preferably CF ₃ ; X ₁ and X ₂ , which are independent from each other, are perfluoroalkyl having a fluorine atom or 1 to 3 carbon atoms, and preferably CF ₃ .

Preferred weight / weight ratios of the three classes of monomers forming the tetrafluoroethylene / perfluoromethylvinylether / fluorine monomer (D) thermoplastic copolymer are as follows:

Perfluoromethyl vinyl ether is 2 to 9% by weight;

Fluorine monomer is 0.1 to 1.5% by weight;

Tetrafluoroethylene consists of the remaining 100% by weight.

Among the comonomers of formula (II), for example, perfluoroethyl vinyl ether, perfluoropropyl vinyl ether and perfluorobutyl vinyl ether can be mentioned. The most preferred comonomer of this class is perfluoropropylvinylether.

Comonomers of formula (III) are described, for example, in European patent application 75,312, in which examples of such comonomers r is 1 or 2 and r 'is 2.

The comonomers of formula (IV) are represented by the formula:

CF ₂ Cl-CFCl-OZ (CFXO) _q- (OCF ₂ -CFY) _{q '} -OT

It is obtained by dechlorination of compounds having.

It may be prepared as described in Example 11 of USP 4,906,770.

In comonomers of formula ( _F ) R _F -CH = CF ₂ , the R _F radical preferably comprises 2 to 6 carbon atoms. Examples of such comonomers are perfluorobutylethylene and perfluorohexylethylene.

The fluorine comonomers of (1) to (3) described above can be copolymerized with TFE and perfluoromethylvinyl ether alone to make a terpolymer, or to each other to make a copolymer having a tetrapolymer or more complex composition. Can be combined.

These tetrafluoroethylene copolymers can be prepared by radical polymerization in an aqueous medium. In particular, it is particularly suitable for carrying out the dispersion in a water-soluble state using microemulsion or dispersion of perfluoropolyethers, according to European patent application 247,379 or preferably USP 4,864,006.

Preferred TFE (co) polymers that can be used to prepare the greases of the present invention are TFE (PTFE) homopolymers or TFE (co) polymers having between 0.05 and 8 mole percent perfluoromethylvinylether. The latter is known as MFA perfluoropolymer.

Melt flow index (hereinafter referred to as MFI) is a common indicator of the weight average molecular weight of polymers. MFI of PTFE or its copolymers (ASTM D1238-52T) may generally range between 0.1 and 30. However, TFE (co) polymers with molecular weights up to 1,000,000 are also suitable.

Perfluoropolyether oils are as follows:

(CF ₂ CF ₂ O), (CF ₂ O), (CF ₂ CF (CF ₃ ) O), (CF (CF ₃ ) O), (CF ₂ CF ₂ CF ₂ O), (CF ₂ CF (OX) ₃ ) O) and a compound comprising a fluoroalkylene unit selected from (CF (OX ₃ ) O) units, wherein X ₃ is-(CF ₂ ) _n CF ₃ , n is 0, 1, 2, 3, 4, wherein the units are distributed statistically in the polymer chain. These end groups are of the fluoroalkyl type, optionally comprising one chlorine and / or hydrogen atom, for example -CF ₃ , -C ₂ F ₅ , -C ₃ F ₇ , ClCF ₂ CF (CF ₃ ) -, CF ₃ CFClCF _2- , ClCF ₂ CF _2- , ClCF _2- , -CF ₂ H, -CF (CF ₃ ) H. For example, neutral perfluoropolyethers can be used, ie they have a viscosity generally comprised between 20 and 4000 cst at 20 ° C. and a weight average molecular weight comprised between 700 and 20,000, with the following classification:

As (a1) a classification T ₁ -O (CF (CF ₃ ) -CF ₂ O) _a (CFXO) _b -T ₂ ,

T ₁ and T _{2, which} may be the same or different from each other, may be a -CF ₃ , -C ₂ F ₅ , -C ₃ F ₇ group, and X is -F or -CF ₃ ; a, b are integers for which the molecular weight is within this range, such perfluoropolyethers are obtained following the procedure described in UK 1,104,482, and continuous of end groups to unreacted groups according to the method described in UK 1,226,366. Has a transition,

(b1) which is the classification CF ₃ -O (CF ₂ CF ₂ O) _c (CF ₂ O) _d -CF ₃ ,

In the above, c, d is an integer for the molecular weight to fall within the above range,

Such PFPE is prepared by C ₂ F ₄ photochemical oxidation according to USP 3,715,378,

(c1) which is the classification C ₃ F ₇ -O (CF (CF ₃ ) -CF ₂ O) _e -T ₃ ,

Wherein T ₃ is —C ₂ F ₅ , —C ₃ F ₇ ; e is the integer whose molecular weight constitutes this range, and these compounds are ionic oligomerization of hexafluoropropene epoxide and a sequence of acylfluoride (COF) with fluorine according to USP 2,242,218. Manufactured by conventional processing,

(d1) is a classification T ₄ -O (CF (CF ₃ ) -CF ₂ O) _g (C ₂ F ₄ O) _h (CFXO) _i -T ₅ ,

In the above, the same or different T ₄ and T ₅ are each a perfluorinated group —CF ₃ , —C ₂ F ₅ , —C ₃ F ₇ ; X is -F or -CF ₃ ; g, h, i are integers for the molecular weight to fall within the above range,

These products are obtained by photooxidation of C ₃ F ₆ and C ₂ F ₄ mixtures and by continuous treatment with fluorine according to the method described in USP 3,665,041,

(e1) Classification is T ₆ -O (CF ₂ CF ₂ CF ₂ O) ₁ -T ₇ ,

T ₆ and T ₇ , which are the same or different from each other, are —CF ₃ , —C ₂ F ₅ , —C ₃ F ₇ ; 1 is an integer for the molecular weight to be in the above range,

These products are obtained in accordance with EP 148,482,

(f1) Classification is T ₈ -O (CF ₂ CF ₂ O) _m -T ₉ ,

T ₈ and T ₉ , which are the same as or different from each other, are a -CF ₃ , -C ₂ F ₅ group; m is selected from classifications in which the molecular weight is an integer to fall within the range.

These products have perfluoroalkyl end groups selected from those obtained according to USP 4,523,039.

(Per) fluoropolyethers with chlorinated end groups can be obtained, for example, as described in USP 5,051,158.

(Per) fluoropolyethers with hydrogenated end groups are prepared according to EP 695,775.

Preferred (per) fluoropolyethers are those of the above categories a1), b1), d1) having a viscosity of 1,000 to 3,000 cst, preferably 1,200 to 2,000 cst.

Fluorine surfactants with perfluoropolyether or perfluoroalkyl chains can be both ionic and nonionic. It is also possible to use surfactant mixtures. In particular, as a functional part suitably connected to a fluorine chain, it is as follows.

A ') mono and dicarboxylic acids and salts thereof;

B ') sulfonic acid and salts thereof;

C ') phosphoric esters and salts thereof with one or two hydrophobic chains; See for example European Patents EP-687,533 and EP-709,517;

D ') nonionic surfactants with fluorine chains and polyoxyalkylene chains; This may be referred to the European patent applications EP 97,111,448.3, EP 97,111,447.5 and EP 97,114,418.3 mentioned in this application;

E ') mention may be made of cationic surfactants having 1,2 or 3 hydrophobic chains.

Carboxylic surfactants having a weight average molecular weight of less than 600 and having a perfluoropolyether chain are preferably used, with a perfluoropolyether chain having a1) classification.

Anticorrosive and / or wear resistant agents are known in the prior art, such as USP 4,472,290, USP 5,000,864 and EP 687,533 and EP 709,517.

Preferred fluorine greases of the present invention which exhibit a mixture of improved properties can be obtained by the method described below.

Another feature of the invention is at least the following steps:

obtaining a dispersion that is a starting material by a polymerization process in a water-soluble state, which is a ');

b ') adding 50 to 500 mg, preferably 100 to 300 mg, per gram of polymer to the (per) fluoropolymer based on TFE in the water-soluble matrix of the surfactant;

Perfluoropolyether oil having a boiling point of less than 5 cst at 25 ° C. and a boiling point not higher than 150 ° C. or a fluorocarbon having a boiling point lower than 150 ° C. is added to the aqueous matrix of step b ′). Thereby making the weight ratio of polymer / oil lower than 0.5, preferably between 0.3 and 0.1;

perfluoro with a viscosity comprised between 20 and 4000 cst at 20 ° C. in an amount to obtain a final grease comprised between 15 and 50% by weight, preferably between 22 and 30% by weight, of the polymer in step d '). Adding a polyether;

at a temperature comprised between 50 and 90 ° C. under vacuum, step e ′), a method for producing fluorine grease having the above-mentioned characteristics comprising the step of completely evaporating the low boiling component.

Antirust and wear resistant additives known in the art may be used to further improve the properties mentioned in, for example, USP 4,472,290 and USP 5,000,864. Such additives may be added at any stage included in the process of the invention. In particular, the final grease has more homogenization distribution when adding the additives to any of the steps b ')-d').

Low boiling components, ie water, low boiling perfluoropolyethers or other (per) fluorocarbons and optionally surfactants can be recovered by concentration.

The surfactants or dispersions used in step b ') have properties such as wear resistance and / or rust prevention. In this case, it is not necessary to administer other additives.

The (per) fluoropolymers in the water-soluble matrix mean latexes obtained by a polymerization process using water as a reaction medium, preferably latexes obtained by an emulsion process, and more preferably microemulsion Latex obtained by the process, see for example USP 4,864,006 and USP 4,789,717.

Another feature of the present invention is that the process can be simplified if a suspension process, ie a dispersion of fluoropolymers obtained by employing a fluorine solvent, is used or mixed with perfluoropolyethers. In this method, the steps a ') to c') are omitted.

The surfactants in step b ′) can be added purely or in a hydroalcoholic solution and / or suspension.

The perfluoropolyether oils of steps c ') and d') are compounds having a viscosity value within the range indicated in the steps of the method and having the above-described structure.

In addition, instead of the perfluoropolyether of step c ′), a corresponding structure in which one or both terminal groups contain hydrogen atoms may be used. Such structures can refer to European patent application EP 97,103,590.2, which describes the structure of various compounds with hydrogenated end groups. In addition, instead of the perfluoropolyether of step c '), perfluorocarbons optionally containing heteroatoms such as O and N and having a viscosity similar to that of the perfluoropolyether of step c') may be used. .

After addition of the perfluoropolyether oil in step c '), depending on the surfactant used, in a dispersion of water / oil in a mixed state or in oil with optionally separable surnatant water A polymer dispersion of can be obtained. In order to reduce the emulsification of water in oil and vice versa and to facilitate its recovery, a method of selecting a surfactant according to the prior art is known. However, this method does not affect the method of the present invention.

By means of photodispersion, the acquisition of a system in the transfer of oil or in a mixture of water / oil on the sample properly diluted with the same oil as in step c ') is overall for the aqueous dispersion of step b'). It is confirmed that it does not involve a substantial variety of polymer sizes.

Acquiring the emulsion or separation of water and oil in step C ') does not affect the properties of the obtained grease. However, this method can also be performed in the case of complete emulsification of the system.

Preferably the water-soluble matrix of the (per) fluoropolymer in step b ') is obtained by a gelling process, neutralization and gel dispersion of the water-soluble latex of step a').

This method is at least as follows:

gel formation step by the addition of the electrolyte a)), in the case of inorganic monovalent electrolytes, the concentration of gel required for complete gelling is higher than 10 ^-3 moles, for example inorganic mono-monovalent electrolytes such as nitric acid (inorganic uni-univalent electrolytes) or sodium nitrate is preferably used, and when gelling with nitric acid, it is preferable to perform at a pH of 0.5 and 2,

This gel formation can be carried out with the precipitation of the electrolyte solution in a static condition on the latex surface, or with light stirring to avoid coagulation.

step b '') is the step of neutralizing the gel with dilute alkaline solution (e.g. 10 ^-4 moles of NaOH) to a final pH of 6-7 pH and washing with water continuously;

step c '') redisperses the gel with the aforementioned surfactants, preferably sodium or potassium carboxylates, phosphate esters, more preferably sodium and potassium carboxylates, having a weight average molecular weight no greater than 600. Steps.

This surfactant can be added to the gel and, if liquid, both in water-soluble or hydroalcohol solutions and / or dispersions at concentrations between 10 and 90% by weight.

The amount required for gel redispersion is between 50 and 500 mg per gram of polymer.

By the use of carboxyl surfactants with perfluoropolyether chains whose weight average molecular weight is not greater than 600, it is possible to limit the contents of the final grease (less than 3.5% by weight), predominantly in water during step c '). It can be separated, and the water-soluble state can be almost completely separated from the low viscosity fluorine oil in step c ').

The most suitable surfactant depending on the above case can be selected according to the prior art.

The dispersion obtained from the gel forms a (per) fluoropolymer in the water-soluble matrix described above in step b ') in the grease preparation method described above.

In this method, when the gelling step is used, the transfer [c ') step of the polymer based on TFH from the water-soluble state to the organic fluorine state is higher.

That is, in step c ') in the general method there is a partial or total transfer of polymer particles from the water-soluble state to the fluorine state.

The following examples are intended to illustrate the purpose of the invention, but not to limit the invention.

Example

a. Water Soluble Dispersion by Gel Redispersion

Example 1

The latex used comprises a terpolymer formed by mixing TFE, FMVE, FPVE in a molar ratio of 96.15: 3.5: 0.35, and was prepared according to the method described in Example 1 of EP 623,274. The size of this polymer particle is 75 nm in average diameter. The latex obtained has a concentration of 30.8% by weight of the polymer.

Glass colum (length: 22 cm, diameter: 4 cm) with a porous separator (G2 type: pore diameter: 40-100 microns) at the bottom, pre-wet 220 g of latex with 0.32 M HNO ₃ solution Put on. Then, at pH 1, 6.8 ml of 6.8 M nitric acid having about 200 ml of gelled preparation is acidified by administration from above. The bottom of this column is then connected with a tank containing 10 ⁻³ M NaOH solution. This NaOH solution is pressed through the column by a recharging metering pump (volume of 50 ml) operating at 60 ml / hr. The front of the column was connected to the tank for recovery of the solution pressed from the bottom by the pump.

The gel was neutralized with 10 ^-3 M NaOH solution (27 doses per 50 ml each) to a final pH of 6, and then the contents of NO ₃ ^-1 ions were dissolved in 250 ml of distilled water. Measured by ion chromatography and washed to 5 ppm. The polymer contained in the gel was 30% by weight.

In order to obtain a dispersion of the total polymer particles in water-soluble state with an average diameter of less than 400 nm with a wide dimensional distribution comprising 75 nm polymer initial particles, the non-ionic S1 in the gel state 81.2 g of an aqueous solution with 25% by weight of the dispersing surfactant are added. The nonionic S1 dispersing surfactant is as follows:

Has a chemical formula such as s + t = 2.5,

R _F3 is R _F2 O (CF (CH ₃ ) -CH ₂ O) _{n '} (CF (CH ₃ ) O) _p' (CH ₂ O) _{m '} CH ₂

R _F3 has a weight average molecular weight of 650 and R _F2 is a perfluoroalkyl having 1 to 3 carbon atoms. The composition of the dispersion obtained is configured to have 300 mg of surfactant S1 per gram of polymer.

Example 1 was repeated by replacing the nitric acid solution with sodium nitrate with a similar concentration in the gelling step to reduce the dose number of sodium hydroxide 10 ⁻³ M and to obtain a gel with pH 6.7.

Example 2

Example 1 was repeated using the same latex, but the water-soluble solution of the nonionic surfactant S1 had the end group R _F4 = ClC ₃ F ₆ instead of the end group R _F2 , and the above-mentioned perfluoropoly of R _F3 type The sodic salt of carboxylate with ether chain was replaced with 27.2 g of an aqueous solution with 25% by weight. Such a surfactant had a weight average molecular weight of 426 and was defined as S2.

The composition of the dispersion obtained consists of 100 mg of surfactant per gram of polymer.

Example 3

Example 1 was repeated using the same latex, but the aqueous solution of nonionic surfactant S1 had a structure and terminal group similar to that of S2. A weight average molecular weight of 530 was coped with 34 g of an aqueous solution having 20% by weight of the ammonium salt of carboxylate.

This surfactant, employed in Example 3, was defined as S3.

The composition of the dispersion obtained consists of 100 mg of surfactant S3 per gram of polymer.

Example 4

PTFE latex prepared according to the polymerization process in microemulsion according to USP 4,864,006 was used.

The polymer included in the latex was 14.4 wt% and the average diameter of the particles was 70 nm.

216 g of latex was treated as in Examples 1-3, and the final gel state at pH 7 had 17.6% by weight of polymer.

To this gel state was added 37.2 g of a 25% aqueous solution of the nonionic surfactant S1, having 300 mg of surfactant per gram of polymer and having a dimensional distribution of less than 400 nm, containing a width of 70 nm initial particles. A dispersion in the water-soluble state of the total polymer particles having an average diameter was obtained.

Example 5

Without the use of perfluoropolyethers, PTFE latexes prepared for the polymerization process in aqueous dispersion according to USP 4,789,617 were used.

Latex is formed by particles having the same diameter of about 0.2 microns and has a dry powder concentration of 27.2% by weight.

300 g of the latex was treated as in Example 1-3. The final gel state at pH 7.5 has 37.5% by weight of polymer.

To this gel state, 97.9 g of a 25% aqueous solution of the nonionic surfactant S1 was added and a dispersion of particles in the overall water soluble state with an average diameter smaller than microns, with a width dimensional distribution comprising polymer initial particles. Obtained.

b. Dispersion in Fluorine Oils with Low Viscosity and Low Boiling Point

Example 6

To 307.1 g of the aqueous dispersion obtained according to example 1, 271 g of Galden ^R HT 70 (Ausimont), belonging to the above a1) classification, with a boiling point of 70 ° C. and a viscosity of 0.5 cst at 25 ° C. was added. This polymer / oil ratio was 0.25 (weight / weight).

By shaking by hand, these polymer particles were transferred from a water-soluble state to fluorine oil. After about 4 hours of decantation, a saturated state of water was obtained.

The polymer dispersion obtained in oil is 19.4% by weight of the polymer (which corresponds to 99.8% of the initial polymer), 0.8% by weight of the nonionic surfactant S1 (which corresponds to 13% of the initial amount of S1), 2 The amount of remaining water equal to% by weight (Karl Fischer titration) and 77.8% by weight of Galden ^R oil HT 70 was included.

The final dispersion was formed of particles having a width dimensional distribution comprising polymer initial particles of 75 nm and having an average diameter of less than 500 nm.

This isolated water-soluble state was dried at 80 ° C. to recover about 87% of the initial amount of nonionic surfactant S1.

Example 7

A 1 L glass separation funnel was administered 279.2 g of the same latex as the aqueous latex of Examples 1-3, comprising 103.2 g of an aqueous solution with 30.8% by weight of polymer and 25% by weight of non-ionic surfactant S1 described above. .

After homogenization, the same water soluble dispersion with 344 g of Galden oil as in Example 6 was added and shaken by hand. This polymer / oil ratio (weight / weight) was 0.25.

The water / oil / polymer dispersion is decanted for 20 hours, which is the heavier state, which is predominantly formed by Galden ^R oil HT 70 and contains 20% of the initial polymer amount in water-soluble latex. State; The polymer had a concentration of 29% by weight and was isolated in a energetically close state to the initial state in latex.

The efficiency of the polymer transfer from water to fluorine oil is acceptable, but this is much lower than that obtained by gelation of the same latex used in Example 6. The isolated oily state comprises, at 5% by weight of the polymer, 0.9% of the nonionic surfactant S1, which corresponds to 13.9% of the amount of surfactant in the initial latex.

Example 8

To the aqueous dispersion obtained in Example 2 was added 271 g of Galden ^R oil HT 70.

By operating as in Example 6, 19.5% by weight of the polymer (which corresponds to 99.4% of the initial polymer), 0.6% by weight of the aforementioned carboxyl surfactant S2 (corresponding to 30% of the initial S2 amount), 1.2 A polymer dispersion in oil was obtained, comprising 78.7% by weight of fluorine oil and the amount of remaining water equal to% by weight (Kar Fischer titration).

This isolated serpentant water-soluble state was dried at 80 ° C. to obtain about 70% of the amount of surfactant S2 initially added.

Example 9

To the aqueous dispersion obtained in Example 3 was added 271 g of Galden ^R oil HT 70.

By operating as in Example 6, 19.5% by weight of the polymer (which corresponds to 99.4% of the initial polymer), 0.6% by weight of the aforementioned carboxyl surfactant S3 (corresponding to 30% of the initial S3 amount), 1.2 A polymer dispersion in oil was obtained, comprising 78.7% by weight of fluorine oil and the amount of remaining water equal to% by weight (Kar Fischer titration).

This isolated energetically water-soluble state was dried at 80 ° C. to recover about 70% of the amount of surfactant S3 initially added.

Example 10

To the water-soluble dispersion obtained according to example 4, 155.5 g of Galden ^R oil HT 70, having a polymer / oil ratio of 0.2 (weight / weight), was added.

By operating as in Example 6, 16.2% by weight of the polymer (which corresponds to 99.8% of the initial polymer), 0.7% by weight of the nonionic surfactant S1 (corresponding to 14% of the initial S1 amount), 1.8% by weight A polymer dispersion in oil was obtained, comprising the same amount of remaining water as Karl Fisher's titration and 81.3% by weight of fluorine oil.

This isolated energetically soluble state was dried at 80 ° C. to recover about 86% of the amount of surfactant initially added.

Example 11

To 315.5 g of the water soluble dispersion obtained according to Example 5, comprising the aforementioned nonionic surfactant S1, 408 g of Galden ^R oil HT 70, corresponding to 0.2 (weight / weight) of polymer / oil ratio, was added.

Except for obtaining a water soluble state after about 12 hours of decantation, it was operated in the same manner as in Example 6, with 13.4% by weight of the polymer (corresponding to 80% of the initial polymer) and 1% by weight of surfactant S1 (initial) 20% of the amount of S1), the amount of remaining water equal to 2% by weight (Karl Fischer titration) and 83.6% by weight of fluorine oil were obtained polymer dispersion in oil.

c. Grease manufacturer

Example 12

To the polymer dispersion in Galden ^R oil HT 70, prepared according to Example 6 using the material of Example 1 as starting material and comprising 67.62 g of a polymer and 2.64 g of a nonionic surfactant S1, 141.05 g of Fomblin ^R oil YR (Ausimont), which was included and had a viscosity of 1500 cst at 20 ° C., were added to have 32 weight percent polymer based on the total weight of polymer, Fomblin ^R oil YR and surfactant.

The dispersion obtained is poured into a 2 L flask. The flask was connected to a rotorvapor Heidolph-2001 operating at 130-160 rpm at a residual pressure of 10 mmHg and with a thermostatic bath at 55 ° C. ^The dispersion fraction was formed by ^R oil HT 70 and the remaining water in the dispersion was removed from the sample and recondensed. As with water removal (checked by Karl Fischer titration), recovery of Galden ^R oil HT 70 was complete.

The homogenization state remaining in the flask was formed by 32 weight percent polymer, 1.3 weight percent nonionic surfactant S1 and 66.7 weight percent Fomblin ^R oil YR. Cool at room temperature and then sample for lubrication measurements.

The results are shown in Table 1, and all values in the table refer to tests performed under the following reference conditions.

Wear diameter: ASTM D2266 (run at 75 ° C. or 250 ° C. for 1 hour; load 40 kg; rotate at 1200 rpm);

Oil separation: FTMS 791-321 (performed at 204 ° C. for 30 hours);

Viscosity: ASTM D2595 (performed at 204 ° C. for 22 hours)

Example 12 was repeated by replacing Fomblin ^R oil YR with oil having the same viscosity but with structure b1).

Example 13

Example 12 was repeated, but to the same dispersion containing the polymer and nonionic surfactant S1 in Galden ^R oil HT 70, the same Fomblin ^R oil YR was added (171.2 g), so the polymer, Fomblin ^R oil It had 28 weight percent polymer relative to the total weight of YR and surfactant S1.

The obtained dispersion was treated according to Example 12 to fully recover Galden ^R oil HT 70, remove residual water, and 28% polymer, 1.1% by weight of nonionic surfactant S1 and Fomblin ^R oil A homogenization state formed of 70.9% by weight of YR was obtained. The characteristics of this grease are shown in Table 1.

With a portion of this sample, an EP test was conducted according to the IP239 standard, obtaining 117 kg as Hertz load value and 200 kg as starting welding load value.

Example 14

Example 13 was repeated with the same conditions and the same material by increasing the evaporation temperature of the low boiling component up to 90 ° C.

A homogenization dispersion formed of 28% by weight of polymer, 1.1% by weight of nonionic surfactant S1 and 70.9% by weight of Fomblin ^R oil YR was obtained.

Removal of components with low boiling point was complete and faster than in Example 13.

Data relating to the specificity of the grease obtained is shown in Table 1, which shows a substantial unchange of the weir diameter for Example 13.

Example 15

In a polymer dispersion in Galden ^R oil HT 70 prepared according to Example 8 using the material of Example 2 as starting material and comprising 67.35 g of polymer and 2.04 g of carboxyl surfactant S2, Example 12-. As in 14, 159.1 g of the same Fomblin ^R oil with high viscosity were added.

The dispersion obtained was poured into a 2 L flask and 12 g of Fomblin ^R DA305 additive with the properties described in US patent application USP 5,000,864 were added.

Operating in the same manner as in Example 12, by obtaining a grease comprising 28% by weight polymer, 0.9% by weight carboxyl surfactant S2, 5% by weight Fomblin ^R DA305 additive and 66.1% by weight of Fomblin ^R oil YR, The boiling components were completely removed.

After cooling this sample at room temperature, a lubrication test was carried out and the results are shown in Table 1.

In addition, as part of this sample, an Emchor test was conducted according to DIN 51802, which obtained classification 0, which meant no overall corrosion.

Example 16

Example 15 was repeated under the same material and under the same conditions, but the Fomblin ^R DA305 additive was prepared with the same perfluoropolyether chain of the phosphate ester type, having the properties described in EP 687,533 and having the following general structure (A1). Replace with amount (12 g) of additive. The general structure (A1) is as follows.

R _F5 -CH _2- (OCH ₂ CH ₂ ) _1,5 -O-PO- (OH) ₂ (A1)

In the above, R _F5 is R _F2 O (CF (CH ₃ ) -CH ₂ O) _{n '} (CF (CH ₃ ) O) _P' (CF ₂ O) _{M '} CF ₂ , R _F5 is the weight average molecular weight 2900 R _F2 has 1 to 3 carbon atoms.

It works as in Example 15 to complete the recovery of low boiling components, 28% by weight of polymer, 0.9% by weight of carboxyl surfactant S2, 5% of additive (A1) and of Fomblin ^R oil YR Grease formed at 66.1% was obtained. After cooling this at room temperature, the sample was lubricated, and the result is shown in Table 1.

In addition, as part of this sample, an Emchor test was conducted according to DIN 51802, which obtained classification 0, which meant no overall corrosion.

Example 17

Example 15 was repeated with the same material and under the same conditions, but Fomblin ^R DA305 additive was replaced with 9.54 g of a 25.2 wt% benzotriazole solution. This benzotriazole solution is 1: 1.4 (weight / weight) of isopropanol and a low boiling point perfluoropolyether oil having a weight average molecular weight of 220 and a1) category containing a hydroxyl terminal group corresponding to 9050 ppm of H. Mixed mixture.

Operating in the same manner as in Example 15, the complete recovery of the low boiling component with isopropanol, 27.8% by weight of the polymer, 0.8% by weight of the carboxyl surfactant S2, 1% of benzo-triazole and Fomblin ^R Grease containing 70.4% of oil YR was obtained. A lubrication test was carried out with this sample, and the results are shown in Table 1.

Benzotriazoles, known in the art, are hydrocarbon type corrosion inhibitors, do not dissolve in Fomblin ^R oil YR, and are not chemically compatible with water. In grease, which is the object of the present invention, the diffusion of benzotriazole is readily obtained in step c ') of the production process, as described above, and after separation of the water soluble sustainant layer, the homogeneity of the dispersion compared to similar conventional greases Improved.

Example 18

Fomblin ^R oil, prepared in accordance with Example 9 using the material of Example 3 as starting material, in a polymer dispersion in Galden ^R oil HT 70 comprising 67.35 g of polymer and 2.04 g of ammonia salt of surfactant S3 described above. 171.1 g of YR were added. In fact, Example 13 is repeated with another surfactant.

Working as in Example 12, the low boiling components were completely removed from the sample.

The grease obtained was formed from 28% by weight of the polymer, 0.9% by weight of the carboxyl surfactant S3 and 71.1% by weight of Fomblin ^R oil YR. After cooling at room temperature, a lubrication test was carried out with this sample, and the results are shown in Table 1.

Example 19 (Comparative Example)

8.11 kg of the same latex as latex used in Example 1 was coagulated by deformation, and the powder obtained was washed with distilled water until pH 6 and then dried in a stove at 220 ° C. for 20 hours.

To obtain 32% by weight of polymer in comparative grease, 2 kg of the dry powder was treated according to Example 1 of USP 4,472,290 using the same oil as Fomblin ^R oil YR of Example 12. Except for the surfactant, the composition obtained here is identical to the grease for the purpose of the present invention, which is Example 12.

As can be seen from the results of the wear test in Table 1, this grease made according to the prior art had a higher wear diameter than the grease made in Example 12. From the data in Table 1, it can be seen that the grease according to the invention determines a 48% improvement in the lubrication powder.

Example 20 (comparative example)

2 kg of the same dry powder as that of Example 19 was treated according to Example 1 of USP 4,472,290 using the same oil as the Fomblin ^R oil YR of Example 13 and a nonionic surfactant S1 to give a composition (% by weight). This was followed by: 28 polymers, 1.1 surfactant and 70.9 Fomblin ^R oil YR. This composition obtained according to the prior art is identical to that prepared according to Example 13 of the present invention.

As can be seen from the results of the weir test of Table 1, the grease of this comparative example is clearly measured by a higher weir diameter than that of the grease produced in Example 13. From Table 1, it can be seen that the grease according to the invention determines a 113% improvement in lubrication powder.

Example 21 (comparative example)

2 kg of the same dry powder as in Example 19 was treated according to Example 1 of USP 4,472,290, using the same Fomblin ^R oil YR, the same carboxyl surfactant S2 and the same additive Fomblin ^R DA305, as in Example 15 , A composition consisting of 28 polymers, 0.9 surfactant S2, 5 Fomblin ^R DA305 additive and 66.1 Fomblin ^R oil YR was obtained.

Samples obtained according to the prior art having the same composition as prepared according to the invention of Example 15 have a viscosity much lower than that of the preparation of Example 15 and the grease of the object of the invention. In addition, as can be seen from the results of the oil separation test according to FTMS 791-321 (tested at 204 ° C. for 30 hours), the grease of Example 15 was prepared according to the prior art, compared to the oil separation value of 11.2% by weight. Since the oil separation value of the sample thus obtained is 30% by weight, the sample shows clearly lower stability than the corresponding preparation made according to the present invention (Example 15), in terms of oil decomposition.

Thus, this sample does not exhibit stability due to high oil separation and therefore does not perform a wear test.

Example 22

Fomblin in 185.2 g of the dispersion of the polymer in Galden ^R oil HT 70, prepared according to Example 10 using the material of Example 4 as starting material and comprising 30 g of homopolymer and 1.29 g of nonionic surfactant S1 75 g of ^R oil YR was added.

By operating as in Example 12, the low boiling components were completely removed.

The obtained homogenization state, formed of 24% by weight of polymer, 1% by weight of nonionic surfactant S1 and 75% by weight of Fomblin ^R oil YR, was cooled at room temperature and the lubricity was measured. The results are shown in Table 1.

Example 23 (comparative example)

6.94 kg of the latex of the homopolymer was solidified by deformation, which is the same as the latex of the homopolymer used in Example 4, and forms the starting material for preparing the grease of Example 22. The obtained powder was washed with distilled water until pH 6.8 and then dried for 20 hours in a stove at 220 ℃.

500 g of dry powder were treated according to Example 1 of USP 4,472,290 using 1.56 kg of Fomblin ^R oil YR and 20.8 g of non-ionic surfactant S1 as in Example 22, to give a grease having the same final composition as in Example 22. Obtained.

The lubricity of the grease obtained according to the prior art was measured, and the results are shown in Table 1.

This sample, prepared according to the prior art but having the same composition as in Example 22, has a higher weir diameter compared to the inventive grease of Example 22, and shows a reduction of about 30% of lubrication powder.

Example 24

450 g of homopolymer in Galden ^R oil HT 70, prepared according to Example 11 using the material of Example 5 as a starting material, comprising 13.4% by weight of homopolymer and 1% by weight of nonionic surfactant S1 To the dispersion, 68.2 g of Fomblin ^R oil YR was added. This example uses a homopolymer with apparently larger initial particles compared to that of Example 22.

According to the preparation of Example 12, after complete removal of the low boiling component, the grease comprising 45.3% by weight of the homopolymer, 3.4% by weight of the nonionic surfactant S1 and 51.3% by weight of the Fomblin ^R oil YR Obtained.

Table 1 shows the results of the lubrication test of this final grease.

Example 25 (comparative example)

Powder obtained by modifying 3.68 kg of homopolymer latex which is identical to homopolymer latex having initial particles of the same diameter as 0.2 micron used in Example 5 and forms the starting material for preparing the grease of Example 24, Was treated as in Example 23 and dried.

500 g of dry powder was treated according to Example 1 of USP 4,472,290 using 566.2 g of Fomblin ^R oil YR and 37.5 g of nonionic surfactant S1 to obtain a grease having the same composition as in Example 24.

As can be seen from the data in Table 1, the lubricity of the powder having a weir diameter of the grease obtained according to the prior art was 100% lower than the lubricity of the grease prepared in Example 24.

Example 26

To 280 g of the dispersion of the polymer in Galden ^R oil HT 70, prepared according to Example 7 using the same latex as Example 1 and containing 14 g of the polymer and 2.52 g of the nonionic surfactant S1, Fomblin 33.5 g of ^R oil YR were added.

The resulting dispersion was poured into a 1 L flask and treated as directed in Example 12 until complete removal of the low boiling component.

The grease obtained consisted of 28% by weight of the polymer, 5% by weight of the nonionic surfactant S1 and 67% by weight of the Fomblin ^R oil YR. The lubricity of this grease was measured and the results are shown in Table 1.

Example 27 (comparative example)

This example illustrates the need for the use of a surfactant as a dispersant in step b ') of the production process according to the invention, although transfer of the polymer to fluorine oil in the water-soluble state is possible without a surfactant.

In a 20-l glass container, 3.37 kg of the same latex as in Example 1 and 10.32 kg of Galden ^R oil HT 70 were administered so as to have a weight ratio of polymer / oil of 0.1 to 30.8% by weight of the polymer.

After light stirring, a decanted dispersion was obtained for 20 hours. So the three states are: the heaviest, which is predominantly formed by Galden ^R oil HT 70 and comprises 15.3% of the initial polymer in latex; The emulsion is separated into a water soluble state containing 27.2% by weight of the polymer based on the intermediate emulsion state and the total weight of the two states. The polymer concentration in the isolated Galden ^R oil HT 70 is 1.6% by weight.

To 12.5 kg of this dispersion was added 14.9 g of nonionic surfactant S1 and 478.6 g of Fomblin ^R oil YR oil.

The appropriate amount of dispersion thus obtained was treated as in Example 12, in which complete removal of low boiling components was achieved.

The grease obtained was formed from 28% by weight of polymer, 5% by weight of surfactant S1 and 67% by weight of Fomblin ^R oil YR.

The results shown in Table 1 in connection with the wear test have the same composition as in Example 26, but are obtained according to the preparation method which is the object of the present invention, and the grease using the surfactant in step b ') is applied to the grease of Example 26. In comparison, the lubrication powder is reduced by about 120%.

Example Dispersing Surfactant (S) additive Polymer concentration (% by weight) Fomblin ^R oil YR Surfactant concentration (% by weight) Additive Concentration (wt%) Wear (mm) Oil separation (% by weight) Oil viscosity (% by weight) 12 S1 none 32 66.7 1.3 0 1.08 6.2 6 13 S1 none 28 70.9 1.1 0 0.8 8.5 2.8 14 S1 none 28 70.9 1.1 0 One 12 2.3 15 S2 Fomblin ^r da305 28 66.1 0.9 5 0.64 11.2 2.7 16 S2 A1 28 66.1 0.9 5 0.72 18 2.1 17 S2 Benzotriazole 27.8 70.4 0.8 One 1.1 - - 18 S3 none 28 71.1 0.9 0 0.93 8.1 4.1 19 (comparative) none none 32 68 0 0 1.6 7.7 - 20 (comparative) S1 none 28 70.9 1.1 0 1.7 7.2 0.6 22 S1 none 24 75 One 0 1.08 10.9 1.5 23 (comparative example) S1 none 24 75 One 0 1.4 9.9 1.3 24 S1 none 45.3 51.3 3.4 0 One 11.2 11 25 (comparative) S1 none 45.3 51.3 3.4 0 2 - - 26 S1 none 28 67 5 0 0.85 2.6 7.7 27 (Comparative Example) S1 none 28 67 5 0 1.85 12 2.3

According to the present invention, while having the same components as conventional fluorine grease and maintaining the lubricating properties and especially the above-described characteristics of grease based on TFE and PFPE (co) polymers, ASTM D2266: 40 ° C. for 1 hour at 40 ° C. When measured by kg rod and 1200 rpm, a grease exhibiting a low diameter weir value can be provided.

In addition, the present invention can provide a method for producing fluorine grease which reduces the above-mentioned disadvantages that occur in conventional grease production, in particular without the use of finishing in three rotational grinding processes. This greatly simplifies the technology of the fluorine grease preparation, which is a great advantage from an industrial standpoint.

Claims (19)

15 to 50% by weight of a polytetrafluoroethylene or tetrafluoroethylene (hereinafter referred to as TFE) copolymer having monomers wholly or partially fluorine and which are unsaturated with other ethylene; 30-84.5% by weight of perfluoroether oil having a viscosity comprised between 20 and 4000 cst at 20 ° C; 0.5-10% by weight of a surfactant or dispersant having a perfluoropolyether or perfluoroalkyl chain; And At least 0-10% by weight of an anti-corrosion and / or antiwear additive, The wear diameter of conventional fluorine greases in which the (per) fluoropolymer particles or the total thereof based on the TFE have an average size smaller than microns, and the weir diameter values of the fluorine greases having the same composition as above are the same as the components of the preparation. Fluorine grease at least 25% lower compared to the value. The fluorine grease according to claim 1, wherein the fluorine grease contains at least 15-30% by weight of polytetrafluoroethylene or copolymers thereof. The method of claim 1 or 2, wherein TFE homopolymer or TFE copolymer is used for the fluorine grease, wherein the TFE homopolymer or TFE copolymer is: Modifications comprising small amounts generally comprised between 0.01 and 8 mole% of one or more comonomers selected from perfluoroalkylperfluorovinylether, vinyldene fluoride, perfluorophene, chlorotrifluoroethylene Polytetrafluoroethylene; A tetrafluoroethylene thermoplastic copolymer comprising 0.5-13% by weight of perfluoromethylvinylether and 0.05-5% by weight of one or more fluorine monomers selected from perfluoropropylvinylether and / or perfluorodioxol Wherein the perfluorodioxol is preferably of the formula Wherein R ₃ is perfluoroalkyl radical C ₁ -C ₅ , preferably CF ₃ ; X ₁ and X ₂ independently of one another, a perfluoroalkyl having from 1 to 3 carbon atoms or fluorine atom, preferably fluorine, characterized in that CF ₃ Greece. The thermoplastic copolymer of claim 1, wherein the thermoplastic copolymer in fluorine grease is: 2 to 9% of perfluoromethylvinyl ether; Between 0 and 1.5% of a fluorine monomer selected from perfluoropropyl vinyl ether and perfluorodioxol; Fluorine characterized in that tetrafluoroethylene is a tetrafluoroethylene / perfluoroalkylvinylether, preferably perfluoromethylvinylether / fluorine monomer thermoplastic copolymer, having a composition constituting the remainder of 100% Greece. The fluorine grease according to any one of claims 1 to 4, wherein the homopolymer or tetrafluoroethylene copolymer is prepared by radical polymerization in an aqueous medium. 6. The method of claim 5 wherein the homopolymer or tetrafluoroethylene copolymer is prepared by radical polymerization in an aqueous medium using a dispersion of perfluoropolyethers or perfluoropolyether microemulsions. Fluorine grease. 7. The perfluoropolyether oil of claim 1, wherein the perfluoropolyether oil is (CF ₂ CF ₂ O), (CF ₂ O), (CF ₂ CF (CF ₃ ) O), (CF (CF ₃ ) O), (CF ₂ CF ₂ CF ₂ O), (CF ₂ CF (OX) ₃ ) O) and a fluoroalkylene unit selected from (CF (OX ₃ ) O) units, wherein X ₃ is-(CF ₂ ) _n CF ₃ and n is 0, 1, 2, 3 , 4, wherein the units are statistically distributed in the polymer chain, and the end groups are of the fluoroalkyl type, optionally containing one chlorine atom and / or hydrogen atom, -CF ₃ , -C ₂ F ₅ , -C ₃ F ₇ , ClCF ₂ CF (CF ₃ )-, CF ₃ CFClCF _2- , ClCF ₂ CF _2- , ClCF _2- , -CF ₂ H, -CF (CF ₃ ) Fluorine grease, characterized in that selected from H. 8. A fluorine grease according to claim 7, wherein said terminal group is perfluoroalkyl type and has a viscosity comprised between 20 and 4000 cst. The method of claim 7 or 8, wherein the perfluoropolyether is classified as follows: As (a1) a class T ₁ -O (CF (CF ₃ ) -CF ₂ O) _a (CFXO) _b -T ₂ : T ₁ and T _{2, which} may be the same or different from each other, may be a -CF ₃ , -C ₂ F ₅ , -C ₃ F ₇ group, and X is -F or -CF ₃ ; a and b are integers whose molecular weights are comprised in the range of the said viscosity; (b1) as CF ₃ -O (CF ₂ CF ₂ O) _c (CF ₂ O) _d -CF ₃ as: Wherein c and d are integers for the molecular weight to fall within the viscosity range; As (c1) a class C ₃ F ₇ -O (CF (CF ₃ ) -CF ₂ O) _e -T ₃ : Wherein T ₃ is —C ₂ F ₅ , —C ₃ F ₇ ; e is an integer whose molecular weight constitutes the range of said viscosity; As (d1) classification T ₄ -O (CF (CF ₃ ) -CF ₂ O) _g (C ₂ F ₄ O) _h (CFXO) _i -T ₅ : In the above, T ₄ and T ₅ , which are the same or different from each other, are a perfluorinated group —CF ₃ , —C ₂ F ₅ , —C ₃ F ₇ ; X is -F or -CF ₃ ; g, h and i are integers for the molecular weight to fall within the range of the said viscosity; (e1) The classification is T ₆ -O (CF ₂ CF ₂ CF ₂ O) ₁ -T ₇ as: T ₆ and T ₇ , which are the same or different from each other, are a -CF ₃ , -C ₂ F ₅ , -C ₃ F ₇ group; 1 is an integer such that molecular weight is within the range of the viscosity; (f1) Classification is T ₈ -O (CF ₂ CF ₂ O) _m -T ₉ as: T ₈ and T ₉ , which are the same as or different from each other, are a -CF ₃ , -C ₂ F ₅ group; m is selected from the classes wherein the molecular weight represents an integer to fall within the range of the viscosity. 10. The fluorine grease according to claim 9, wherein the (per) fluoropolyethers are those of the category a1) having a viscosity from 1000 to 3000 cst, preferably from 1200 to 2000 cst. The fluorosurfactant according to any one of claims 1 to 10, wherein the fluorosurfactant having perfluoropolyether or perfluoroalkyl chain may be ionic and nonionic, and the functional portion of the fluorine chain is as follows: Mono and dicarboxylic acids and salts thereof; Sulfonic acids and salts thereof; Phosphoric esters and salts thereof with one or two hydrophobic chains; Nonionic surfactants with fluorine chains and polyoxyalkylene chains; Fluorine grease, characterized in that it is selected from cationic surfactants having 1,2 or 3 hydrophobic chains. 12. The surfactant according to claim 11, wherein the surfactant is a carboxyl surfactant having a perfluoropolyether chain having a weight average molecular weight of less than 600, and the perfluoropolyether chain is preferably the a1) type. Fluorine grease. The following steps: obtaining a dispersion that is a starting material by a polymerization process in a water-soluble state, which is a '); b ') adding 50 to 500 mg, preferably 100 to 300 mg, per gram of polymer to the (per) fluoropolymer based on TFE in the water-soluble matrix of the surfactant; Perfluoropolyether oil having a boiling point of less than 5 cst at 25 ° C. and a boiling point not higher than 150 ° C. or a fluorocarbon having a boiling point lower than 150 ° C. is added to the aqueous matrix of step b ′). Thereby making the weight ratio of polymer / oil lower than 0.5, preferably between 0.3 and 0.1; perfluoro with a viscosity comprised between 20 and 4000 cst at 20 ° C. in an amount to obtain a final grease comprised between 15 and 50% by weight, preferably between 22 and 30% by weight, of the polymer in step d '). Adding polyether oil; A process for producing a fluorine grease according to any one of claims 1 to 12, comprising at least a step of completely evaporating a low boiling component at a temperature comprised between 50 and 90 ° C. under vacuum, e '). Way. 14. The wear protection and / or antirust additives can be added to any step of the fluorine grease manufacturing process, in particular in any of b ')-d') steps. A process for producing fluorine grease, characterized in that carried out. 15. The method of claim 14, wherein the surfactant or dispersant used in step b ') is a wear resistant and / or antirust additive. The (per) fluoropolymer in the water-soluble matrix is a latex obtained by a polymerization step using water as a reaction medium, and preferably by an emulsion process. Latexes obtained, more preferably latex obtained by microemulsion or dispersion process. Using a dispersion of fluoropolymers obtained by the process in suspension and the following steps: perfluoropolyether having a viscosity comprised between 20 and 4000 cst at 20 ° C. in an amount to obtain a final grease comprised between 15 and 50%, preferably between 22 and 30%, by weight percent of the polymer in step d '). Adding oil; A process for producing a fluorine grease according to any one of claims 1 to 12, comprising at least a step of completely evaporating a low boiling component at a temperature comprised between 50 and 90 ° C. under vacuum, e '). Way. The method according to any one of claims 13 to 16, wherein the water-soluble matrix of the (per) fluoropolymer of step b ') is subjected to the gelling process, neutralization, and gel dispersion of the water-soluble latex of step a'). Obtained by the following steps: gel formation step by the addition of the electrolyte a)) step, neutralizing the gel with alkaline solution in step b '') and continuously washing with water, and c)) redispersing the gel with the surfactant as in step c)). A grease according to any one of claims 1 to 12 which can be obtained according to any of claims 13 to 18.